Opportunities and challenges in the use of inorganic fullerene-like nanoparticles to produce advanced polymer nanocomposites

Polymer/inorganic nanoparticle nanocomposites have garnered considerable academic and industrial interest over recent decades in the development of advanced materials for a wide range of applications. In this respect, the dispersion of so-called inorganic fullerene-like (IF) nanoparticles, e.g., tungsten disulfide (IF-WS2) or molybdenum disulfide (IF-MoS2), into polymeric matrices is emerging as a new strategy. The surprising properties of these layered metal dichalcogenides such as high impact resistance and superior tribological behavior, attributed to their nanoscale size and hollow quasi-spherical shape, open up a wide variety of opportunities for applications of these inorganic compounds. The present work presents a detailed overview on research in the area of IF-based polymer nanocomposites, with special emphasis on the use of IF-WS2 nanoparticles as environmentally friendly reinforcing fillers. The incorporation of IF particles has been shown to be efficient for improving thermal, mechanical and tribological properties of various thermoplastic polymers, such as polypropylene, nylon-6, poly(phenylene sulfide), poly(ether ether ketone), where nanocomposites were fabricated by simple melt-processing routes without the need for modifiers or surfactants. This new family of nanocomposites exhibits similar or enhanced performance when compared with nanocomposites that incorporate carbon nanotubes, carbon nanofibers or nanoclays, but are substantially more cost-effective, efficient and environmentally satisfactory. Most recently, innovative approaches have been described that exploit synergistic effects to produce new materials with enhanced properties, including the combined use of micro- and nanoparticles such as IF-WS2/nucleating agent or IF-WS2/carbon fiber, as well as dual nanoparticle systems such as SWCNT/IF-WS2 where each nanoparticle has different characteristics. The structure–property relationships of these nanocomposites are discussed and potential applications proposed ranging from medicine to the aerospace, automotive and electronics industries.

Human Factor in Resilience Systems

This paper shows the importance of a holistic comprehension of the Earth as a living planet, where man inhabits and is exposed to environmental incidences of different nature. The aim of the paper here summarized is a reflection on all these concepts and scientific considerations related to the important role of men in the handling of natural hazards. Our Planet is an unstable and dynamical system highly sensitive to initial conditions, as proposed by Chaos theory (González-Miranda 2004); it is a complex organic whole, which responds to minimal variations which can affect several natural phenomena such as plate tectonics, solar flares, fluid turbulences, landscape formation, forest fires, growth and migration of populations and biological evolution. This is known as the “butterfly effect” (Lorenz 1972), which means that a small change of the system causes a chain of events leading to large-scale unpredictable consequences. The aim of this work is dwelling on the importance of the knowledge of these natural and catastrophic geological, biological and human systems so much sensible to equilibrium conditions, to prevent, avoid and mend their effects, and to face them in a resilient way

Influence of different organoclays on the curing, morphology, and dynamic mechanical properties of an epoxy adhesive

The thermal, mechanical, and adhesive properties of nanoclay-modified adhesives were investigated. Two organically modified montmorillonites: Cloisite 93A (C93A) and Nanomer I.30E (I.30E) were used as reinforcement of an epoxy adhesive. C93A and I.30E are modified with tertiary and primary alkyl ammonium cations, respectively. The aim was to study the influence of the organoclays on the curing, and on the mechanical and adhesive properties of the nanocomposites. A specific goal was to compare their behavior with that of Cloisite30B/epoxy and Cloisite15A/ epoxy nanocomposites that we have previously studied. Both C30B and C15A are modified with quaternary alkyl ammonium cations. Differential scanning calorimetry results showed that the clays accelerate the curing reaction, an effect that is related to the chemical structure of the ammonium cations. The three Cloisite/nanocomposites showed intercalated clay structures,the interlayer distance was independent of the clay content. The I.30E/epoxy nanocomposites presented exfoliated structure due to the catalytic effect of the organic modifier. Clay-epoxy nanocompo-sites showed lower glass transition temperature (Tg) and higher values of storage modulus than neat epoxy thermoset, with no significant differences between exfoliated or intercalated nanocom-posites. The shear strength of aluminum joints using clay/epoxy adhesives was lower than with the neat epoxy adhesive. The wáter aging was less damaging for joints with I.30E/epoxy adhesive.

Development of novel melt-processable biopolymer nanocomposites based on poly(L-lactic acid) and WS2 inorganic nanotubes.

The use of tungsten disulphide inorganic nanotubes (INT-WS2) offers the opportunity to produce novel and advanced biopolymer-based nanocomposite materials with excellent nanoparticle dispersion without the need for modifiers or surfactants via conventional melt blending. The study of the non-isothermal melt-crystallization kinetics provides a clear picture of the transformation of poly(L-lactic acid) (PLLA) molecules from the non-ordered to the ordered state. The overall crystallization rate, final crystallinity and subsequent melting behaviour of PLLA were controlled by both the incorporation of INT-WS2 and the variation of the cooling rate. In particular, it was shown that INT-WS2 exhibits much more prominent nucleation activity on the crystallization of PLLA than other specific nucleating agents or nano-sized fillers. These features may be advantageous for the enhancement of mechanical properties and process-ability of PLLA-based materials. PLLA/INT-WS2 nanocomposites can be employed as low cost biodegradable materials for many eco-friendly and medical applications, and the exceptional crystallization behaviour observed opens new perspectives for scale-up and broader applications.

Hydrodynamic forces on heave plates for offshore systems oscillating close to the seabed or the free surface

La energía eólica marina es uno de los recursos energéticos con mayor proyección pudiendo contribuir a reducir el consumo de combustibles fósiles y a cubrir la demanda de energía en todo el mundo. El concepto de aerogenerador marino está basado en estructuras fijas como jackets o en plataformas flotantes, ya sea una semisumergible o una TLP. Se espera que la energía eólica offshore juegue un papel importante en el perfil de producción energética de los próximos años; por tanto, las turbinas eólicas deben hacerse más fables y rentables para ser competitivas frente a otras fuentes de energía. Las estructuras flotantes pueden experimentar movimientos resonantes en estados de la mar con largos períodos de oleaje. Estos movimientos disminuyen su operatividad y pueden causar daños en los componentes eléctricos de las turbinas y en las palas, también en los risers y moorings. La respuesta de la componente vertical del movimiento puede reducirse mediante diferentes actuaciones: (1) aumentando la amortiguación del sistema, (2) manteniendo el período del movimiento vertical fuera del rango de la energía de la ola, y (3) reduciendo las fuerzas de excitación verticales. Un ejemplo típico para llevar a cabo esta reducción son las "Heave Plates". Las heave plates son placas que se utilizan en la industria offshore debido a sus características hidrodinámicas, ya que aumentan la masa añadida y la amortiguación del sistema. En un análisis hidrodinámico convencional, se considera una estructura sometida a un oleaje con determinadas características y se evalúan las cargas lineales usando la teoría potencial. El amortiguamiento viscoso, que juega un papel crucial en la respuesta en resonancia del sistema, es un dato de entrada para el análisis. La tesis se centra principalmente en la predicción del amortiguamiento viscoso y de la masa añadida de las heave plates usadas en las turbinas eólicas flotantes. En los cálculos, las fuerzas hidrodinámicas se han obtenido con el f n de estudiar cómo los coeficientes hidrodinámicos de masa añadida5 y amortiguamiento varían con el número de KC, que caracteriza la amplitud del movimiento respecto al diámetro del disco. Por otra parte, se ha investigado la influencia de la distancia media de la ‘heave plate’ a la superficie libre o al fondo del mar, sobre los coeficientes hidrodinámicos. En este proceso, un nuevo modelo que describe el trabajo realizado por la amortiguación en función de la enstrofía, es descrito en el presente documento. Este nuevo enfoque es capaz de proporcionar una correlación directa entre el desprendimiento local de vorticidad y la fuerza de amortiguación global. El análisis también incluye el estudio de los efectos de la geometría de la heave plate, y examina la sensibilidad de los coeficientes hidrodinámicos al incluir porosidad en ésta. Un diseño novedoso de una heave plate, basado en la teoría fractal, también fue analizado experimentalmente y comparado con datos experimentales obtenidos por otros autores. Para la resolución de las ecuaciones de Navier Stokes se ha usado un solver basado en el método de volúmenes finitos. El solver usa las librerías de OpenFOAM (Open source Field Operation And Manipulation), para resolver un problema multifásico e incompresible, usando la técnica VOF (volume of fluid) que permite capturar el movimiento de la superficie libre. Los resultados numéricos han sido comparados con resultados experimentales llevados a cabo en el Canal del Ensayos Hidrodinámicos (CEHINAV) de la Universidad Politécnica de Madrid y en el Canal de Experiencias Hidrodinámicas (CEHIPAR) en Madrid, al igual que con otros experimentos realizados en la Escuela de Ingeniería Mecánica de la Universidad de Western Australia. Los principales resultados se presentan a continuación: 1. Para pequeños valores de KC, los coeficientes hidrodinámicos de masa añadida y amortiguamiento incrementan su valor a medida que el disco se aproxima al fondo marino. Para los casos cuando el disco oscila cerca de la superficie libre, la dependencia de los coeficientes hidrodinámicos es más fuerte por la influencia del movimiento de la superficie libre. 2. Los casos analizados muestran la existencia de un valor crítico de KC, donde la tendencia de los coeficientes hidrodinámicos se ve alterada. Dicho valor crítico depende de la distancia al fondo marino o a la superficie libre. 3. El comportamiento físico del flujo, para valores de KC cercanos a su valor crítico ha sido estudiado mediante el análisis del campo de vorticidad. 4. Introducir porosidad al disco, reduce la masa añadida para los valores de KC estudiados, pero se ha encontrado que la porosidad incrementa el valor del coeficiente de amortiguamiento cuando se incrementa la amplitud del movimiento, logrando un máximo de damping para un disco con 10% de porosidad. 5. Los resultados numéricos y experimentales para los discos con faldón, muestran que usar este tipo de geometrías incrementa la masa añadida cuando se compara con el disco sólido, pero reduce considerablemente el coeficiente de amortiguamiento. 6. Un diseño novedoso de heave plate basado en la teoría fractal ha sido experimentalmente estudiado a diferentes calados y comparado con datos experimentales obtenidos por otro autores. Los resultados muestran un comportamiento incierto de los coeficientes y por tanto este diseño debería ser estudiado más a fondo. ABSTRACT Offshore wind energy is one of the promising resources which can reduce the fossil fuel energy consumption and cover worldwide energy demands. Offshore wind turbine concepts are based on either a fixed structure as a jacket or a floating offshore platform like a semisubmersible, spar or tension leg platform. Floating offshore wind turbines have the potential to be an important part of the energy production profile in the coming years. In order to accomplish this wind integration, these wind turbines need to be made more reliable and cost efficient to be competitive with other sources of energy. Floating offshore artifacts, such oil rings and wind turbines, may experience resonant heave motions in sea states with long peak periods. These heave resonances may increase the system downtime and cause damage on the system components and as well as on risers and mooring systems. The heave resonant response may be reduced by different means: (1) increasing the damping of the system, (2) keeping the natural heave period outside the range of the wave energy, and (3) reducing the heave excitation forces. A typical example to accomplish this reduction are “Heave Plates”. Heave plates are used in the offshore industry due to their hydrodynamic characteristics, i.e., increased added mass and damping. Conventional offshore hydrodynamic analysis considers a structure in waves, and evaluates the linear and nonlinear loads using potential theory. Viscous damping, which is expected to play a crucial role in the resonant response, is an empirical input to the analysis, and is not explicitly calculated. The present research has been mainly focused on the prediction of viscous damping and added mass of floating offshore wind turbine heave plates. In the calculations, the hydrodynamic forces have been measured in order to compute how the hydrodynamic coefficients of added mass1 and damping vary with the KC number, which characterises the amplitude of heave motion relative to the diameter of the disc. In addition, the influence on the hydrodynamic coefficients when the heave plate is oscillating close to the free surface or the seabed has been investigated. In this process, a new model describing the work done by damping in terms of the flow enstrophy, is described herein. This new approach is able to provide a direct correlation between the local vortex shedding processes and the global damping force. The analysis also includes the study of different edges geometry, and examines the sensitivity of the damping and added mass coefficients to the porosity of the plate. A novel porous heave plate based on fractal theory has also been proposed, tested experimentally and compared with experimental data obtained by other authors for plates with similar porosity. A numerical solver of Navier Stokes equations, based on the finite volume technique has been applied. It uses the open-source libraries of OpenFOAM (Open source Field Operation And Manipulation), to solve 2 incompressible, isothermal immiscible fluids using a VOF (volume of fluid) phase-fraction based interface capturing approach, with optional mesh motion and mesh topology changes including adaptive re-meshing. Numerical results have been compared with experiments conducted at Technical University of Madrid (CEHINAV) and CEHIPAR model basins in Madrid and with others performed at School of Mechanical Engineering in The University of Western Australia. A brief summary of main results are presented below: 1. At low KC numbers, a systematic increase in added mass and damping, corresponding to an increase in the seabed proximity, is observed. Specifically, for the cases when the heave plate is oscillating closer to the free surface, the dependence of the hydrodynamic coefficients is strongly influenced by the free surface. 2. As seen in experiments, a critical KC, where the linear trend of the hydrodynamic coefficients with KC is disrupted and that depends on the seabed or free surface distance, has been found. 3. The physical behavior of the flow around the critical KC has been explained through an analysis of the flow vorticity field. 4. The porosity of the heave plates reduces the added mass for the studied porosity at all KC numbers, but the porous heave plates are found to increase the damping coefficient with increasing amplitude of oscillation, achieving a maximum damping coefficient for the heave plate with 10% porosity in the entire KC range. 5. Another concept taken into account in this work has been the heave plates with flaps. Numerical and experimental results show that using discs with flaps will increase added mass when compared to the plain plate but may also significantly reduce damping. 6. A novel heave plate design based on fractal theory has tested experimentally for different submergences and compared with experimental data obtained by other authors for porous plates. Results show an unclear behavior in the coefficients and should be studied further. Future work is necessary in order to address a series of open questions focusing on 3D effects, optimization of the heave plates shapes, etc.

Unsaturated polyester-poly(epsilon-caprolactone) hybrid nanocomposites: Thermal-mechanical properties

This paper reports on the thermal behavior and mechanical properties of nanocomposites based on unsaturated polyester resin (UP) modified with poly(ɛ-caprolactone) (PCL) and reinforced with an organically modified clay (cloisite 30B). To optimize the dispersion of 30B and the mixing of PCL in the UP resin, two different methods were employed to prepare crosslinked UP–PCL-30B hybrid nanocomposites. Besides, two samples of poly(ɛ-caprolactone) of different molecular weight (PCL2: Mn = 2.103g.mol−1 and PCL50: Mn = 5.104g.mol−1) were used at several concentrations (4, 6, 10 wt%). The 30B concentration was 4 wt% in all the nanocomposites. The morphology of the samples was studied by scanning electron microscopy (SEM). The analysis of X-ray patterns reveals that intercalated structures have been found for all ternary nanocomposites, independently of the molecular weight, PCL concentration and the preparation method selected. A slight rise of the glass transition temperature, Tg, is observed in UP/PCL/4%30B ternary nanocomposites regarding to neat UP. The analysis of the tensile properties of the ternary (hybrid) systems indicates that UP/4%PCL2/4%30B nanocomposite improves the tensile strength and elongation at break respect to the neat UP while the Young modulus remains constant

Thermoplastic Polymer Nanocomposites Based on Inorganic Fullerene-like Nanoparticles and Inorganic Nanotubes

Using inorganic fullerene-like (IF) nanoparticles and inorganic nanotubes (INT) in organic-inorganic hybrid composite, materials provide the potential for improving thermal, mechanical, and tribological properties of conventional composites. The processing of such high-performance hybrid thermoplastic polymer nanocomposites is achieved via melt-blending without the aid of any modifier or compatibilizing agent. The incorporation of small quantities (0.1-4 wt.%) of IF/INTs (tungsten disulfide, IF-WS2 or molybdenum disulfide, MoS2) generates notable performance enhancements through reinforcement effects and excellent lubricating ability in comparison with promising carbon nanotubes or other inorganic nanoscale fillers. It was shown that these IF/INT nanocomposites can provide an effective balance between performance, cost effectiveness, and processability, which is of significant importance for extending the practical applications of diverse hierarchical thermoplastic-based composites.

Water and nitrogen footprint in an irrigated crop under mineral and organic fertilization

In order to establish rational nitrogen (N) application and reduce groundwater contamination, a clearer understanding of the N distribution through the growing season and its balance is crucial. Excessive doses of N and/or water applied to fertigated crops involve a substantial risk of aquifer contamination by nitrate; but knowledge of N cycling and availability within the soil could assist in avoiding this excess. In central Spain, the main horticultural fertigated crop is the melon type ?piel de sapo¿ and it is cultivated in vulnerable zones to nitrate pollution (Directive 91/676/CEE). However, until few years ago there were not antecedents related to the optimization of nitrogen fertilization together with irrigation. Water and N footprint are indicators that allow assessing the impact generated by different agricultural practices, so they can be used to improve the management strategies in fertigated crop systems. The water footprint distinguishes between blue water (sources of water applied to the crop, like irrigation and precipitation), green water (water used by the crop and stored in the soil), and it is furthermore possible to quantify the impact of pollution by calculating the grey water, which is defined as the volume of polluted water created from the growing and production of crops. On the other hand, the N footprint considers green N (nitrogen consumed by the crops and stored in the soil), blue N (N available for crop, like N applied with mineral and/or organic fertilizers, N applied with irrigation water and N mineralized during the crop period), whereas grey N is the amount of N-NO3- washed from the soil to the aquifer. All these components are expressed as the ratio between the components of water or N footprint and the yield (m3 t-1 or kg N t-1 respectively). The objetives of this work were to evaluate the impact derivated from the use of different fertilizer practices in a melon crop using water and N footprint.

Evaluating sustainability and food security of peasant farming systems in Mesoamerican highlands

En las últimas décadas, la agricultura sostenible ha sido objeto de gran interés y debate académico, no sólo en términos conceptuales, sino también en términos metodológicos. La persistencia de la inseguridad alimentaria y el deterioro de los recursos naturales en muchas regiones del mundo, ha provocado el surgimiento de numerosas iniciativas centradas en revitalizar la agricultura campesina así como renovadas discusiones sobre el rol que juega la agricultura como motor de desarrollo y principal actividad para alivio de la pobreza. Por ello, cuando hablamos de evaluar sistemas campesinos de montaña, debemos considerar tanto la dimensión alimentaria como las especificidades propias de los sistemas montañosos como base fundamental de la sostenibilidad. Al evaluar la contribución que han hecho alternativas tecnológicas y de manejo en la mejora de la sostenibilidad y la seguridad alimentaria de los sistemas campesinos de montaña en Mesoamérica, surgen tres preguntas de investigación: • ¿Se está evaluando la sostenibilidad de los sistemas campesinos teniendo en cuenta la variabilidad climática, la participación de los agricultores y las dinámicas temporales? • ¿Podemos rescatar tendencias comunes en estos sistemas y extrapolar los resultados a otras zonas? • ¿Son inequívocamente positivas las alternativas propuestas que se han llevado a cabo? En este trabajo se presentan tres evaluaciones de sostenibilidad que tratan de poner de manifiesto cuáles son los retos y oportunidades que enfrentan actualmente los sistemas campesinos de montaña. En primer lugar, se evalúan tres sistemas de manejo agrícola bajo dos años meteorológicamente contrastantes. Se determinó que durante el año que experimentó lluvias abundantes y temperaturas moderadas, los sistemas de bajos insumos, basados en el uso de abonos orgánicos y rotación de cultivos, obtuvieron los mejores resultados en indicadores ecológicos y similares resultados en los económicos y sociales que el sistema de altos insumos químicos. En el segundo año, con heladas tempranas y sequía invernal, la productividad se redujo para todos los sistemas pero los sistemas más diversificados (en variedades de maíz y/o siembra de otros cultivos) pudieron resistir mejor los contratiempos climáticos. En segundo lugar, se evalúa el grado de conocimiento (percepción) campesino para determinar los factores claves que determinan la sostenibilidad de sus sistemas y su seguridad alimentaria. Se determinó que los principales puntos críticos identificados por los campesinos (tamaño de parcela y pendiente del terreno) afectan de forma significativa a cuestiones de índole económica, pero no son capaces de explicar los desequilibrios alimenticios existentes. Realizando un análisis comparativo entre comunidades que presentaban buenos y malos resultados en cuanto a aporte energético y proteico, se determinó que la seguridad alimentaria estaba relacionada con la sostenibilidad de los sistemas y que concretamente estaba ligada a los atributos de equidad y autonomía. Otro resultado destacable fue que las comunidades más marginales y con mayor dificultad de acceso mostraron mayores niveles de inseguridad alimentaria, pero la variabilidad intergrupal fue muy alta. Eso demuestra que la seguridad alimentaria y nutricional forma parte de un complejo sistema de estrategias de autoabastecimiento ligada a la idiosincrasia misma de cada uno de los hogares. En tercer lugar, se evaluó el desempeño de las escuelas de campo de agricultores (ECAs) en la mejora de la sostenibilidad y la seguridad alimentaria de un sistema campesino de montaña. Para ver el efecto del impacto de estas metodologías a largo plazo, se estudiaron tres comunidades donde se habían implementado ECAs hace 8, 5 y 3 años. Encontramos que el impacto fue progresivo ya que fue la comunidad más antigua la que mejores valores obtuvo. El impacto de las ECAs fue rápido y persistente en los indicadores relacionados con la participación, el acceso a servicios básicos y la conservación de los recursos naturales. El estudio demostró un claro potencial de las ECAs en la mejora general de la sostenibilidad y la seguridad alimentaria de estos sistemas, sin embargo se observó una relación directa entre el aumento de producción agrícola y el uso de insumos externos, lo que puede suponer un punto crítico para los ideales sostenibles. ABSTRACT During the last decades, sustainable agriculture has been the subject of considerable academic interest and debate, not only in conceptual terms, but also in methodological ones. The persistence of high levels of environmental degradation and food insecurity in many regions has led to new initiatives focused on revitalizing peasant agriculture and renewed discussions of the role of sustainable agriculture as an engine for development, environmental conservation and poverty alleviation. Therefore, to assess mountain farming systems, we must consider food dimension and taking into account the specificities of the mountain systems as the foundation of sustainability. When evaluating contribution of technological and management alternative proposals in achieving sustainability and food security for peasant farming systems in Mesoamerican highlands, three research questions arise: • Is sustainability of peasant-farming systems being evaluated taking into account climate variability, participation of farmers and temporal dynamics? • Can we rescue common trends in these systems and extrapolate the results to other areas? • What alternative proposals that have been conducted are unequivocally positives? In this document, we present three evaluations of sustainability that try to highlight the challenges and opportunities that currently face mountain farming systems in Mesoamerica. First, we evaluate the sustainability of three agricultural management systems in two contrasting weather years. We determined that during the first year that exposed heavy rains and moderate temperatures, low-input systems, which are based on the use of organic fertilizers and crop rotation, provided better results in terms of ecological indicators and equal results in terms of economic and social indicators than those achieved using a high chemical input system. In the second year, which featured early frosts and a winter drought, productivity declined in all systems; however, the most diversified systems (in terms of the maize varieties grown and the sowing of other crops) more successfully resisted these climatic adversities. Second, we evaluate the farmers’ perception to determine the key drivers for achieving their sustainability and food and nutritional security. We determined that the key factors identified by farmers (landholding size and slope of cropland) exerted significant impacts on economic disparities but did not explain the malnutrition levels. We compared two contrasting hamlets according to their energy and protein supply, one namely Limón Timoté (LT), which did not present food problems and Limón Peña Blanca (LP), which did exhibit food insecurity. The results showed that FNS is linked to sustainability, and it is primarily related to the sustainability attributes of self-reliance and equity. Although the more marginated and inaccessible community exhibited more food insecurity, food and nutritional security depend upon a complex array of self-sufficiency strategies that remain linked to individual household idiosyncrasies. Third, we evaluated the impact of farmer field schools for improving the sustainability and food security of peasant mountain systems. In order to appreciate the long-term impact, we studied three communities where FFSs were implemented eight, five and three years ago, respectively. We found that FFSs have a gradual impact, as the community that first implemented FFSs scores highest. The impact of FFSs was broad and long-lasting for indicators related to participation, access to basic services and conservation of natural resources. This study demonstrates the potential of FFSs, but more attention will have to be paid to critical indicators in order to scale up their potential in the future. We observed a direct relationship between the increase in agricultural production and the use of external inputs, which is a critical point for sustainable ideals.

Agricultural use of organic wastes as source of nitrogen and phosphorus: risks and opportunities

El nitrógeno (N) y el fósforo (P) son nutrientes esenciales en la producción de cultivos. El desarrollo de los fertilizantes de síntesis durante el siglo XX permitió una intensificación de la agricultura y un aumento de las producciones pero a su vez el gran input de nutrientes ha resultado en algunos casos en sistemas poco eficientes incrementando las pérdidas de estos nutrientes al medio ambiente. En el caso del P, este problema se agrava debido a la escasez de reservas de roca fosfórica necesaria para la fabricación de fertilizantes fosfatados. La utilización de residuos orgánicos en agricultura como fuente de N y P es una buena opción de manejo que permite valorizar la gran cantidad de residuos que se generan. Sin embargo, es importante conocer los procesos que se producen en el suelo tras la aplicación de los mismos, ya que influyen en la disponibilidad de nutrientes que pueden ser utilizados por el cultivo así como en las pérdidas de nutrientes de los agrosistemas que pueden ocasionar problemas de contaminación. Aunque la dinámica del N en el suelo ha sido más estudiada que la del P, los problemas importantes de contaminación por nitratos en zonas vulnerables hacen necesaria la evaluación de aquellas prácticas de manejo que pudieran agravar esta situación, y en el caso de los residuos orgánicos, la evaluación de la respuesta agronómica y medioambiental de la aplicación de materiales con un alto contenido en N (como los residuos procedentes de la industria vinícola y alcoholera). En cuanto al P, debido a la mayor complejidad de su ciclo y de las reacciones que ocurren en el suelo, hay un mayor desconocimiento de los factores que influyen en su dinámica en los sistemas suelo-planta, lo que supone nuevas oportunidades de estudio en la evaluación del uso agrícola de los residuos orgánicos. Teniendo en cuenta los conocimientos previos sobre cada nutriente así como las necesidades específicas en el estudio de los mismos, en esta Tesis se han evaluado: (1) el efecto de la aplicación de residuos procedentes de la industria vinícola y alcoholera en la dinámica del N desde el punto de vista agronómico y medioambiental en una zona vulnerable a la contaminación por nitratos; y (2) los factores que influyen en la disponibilidad de P en el suelo tras la aplicación de residuos orgánicos. Para ello se han llevado a cabo incubaciones de laboratorio así como ensayos de campo que permitieran evaluar la dinámica de estos nutrientes en condiciones reales. Las incubaciones de suelo en condiciones controladas de humedad y temperatura para determinar el N mineralizado se utilizan habitualmente para estimar la disponibilidad de N para el cultivo así como el riesgo medioambiental. Por ello se llevó a cabo una incubación en laboratorio para conocer la velocidad de mineralización de N de un compost obtenido a partir de residuos de la industria vinícola y alcoholera, ampliamente distribuida en Castilla-La Mancha, región con problemas importantes de contaminación de acuíferos por nitratos. Se probaron tres dosis crecientes de compost correspondientes a 230, 460 y 690 kg de N total por hectárea que se mezclaron con un suelo franco arcillo arenoso de la zona. La evolución del N mineral en el suelo a lo largo del tiempo se ajustó a un modelo de regresión no lineal, obteniendo valores bajos de N potencialmente mineralizable y bajas contantes de mineralización, lo que indica que se trata de un material resistente a la mineralización y con una lenta liberación de N en el suelo, mineralizándose tan solo 1.61, 1.33 y 1.21% del N total aplicado con cada dosis creciente de compost (para un periodo de seis meses). Por otra parte, la mineralización de N tras la aplicación de este material también se evaluó en condiciones de campo, mediante la elaboración de un balance de N durante dos ciclos de cultivo (2011 y 2012) de melón bajo riego por goteo, cultivo y manejo agrícola muy característicos de la zona de estudio. Las constantes de mineralización obtenidas en el laboratorio se ajustaron a las temperaturas reales en campo para predecir el N mineralizado en campo durante el ciclo de cultivo del melón, sin embargo este modelo generalmente sobreestimaba el N mineralizado observado en campo, por la influencia de otros factores no tenidos en cuenta para obtener esta predicción, como el N acumulado en el suelo, el efecto de la planta o las fluctuaciones de temperatura y humedad. Tanto el ajuste de los datos del laboratorio al modelo de mineralización como las predicciones del mismo fueron mejores cuando se consideraba el efecto de la mezcla suelo-compost que cuando se aislaba el N mineralizado del compost, mostrando la importancia del efecto del suelo en la mineralización del N procedente de residuos orgánicos. Dado que esta zona de estudio ha sido declarada vulnerable a la contaminación por nitratos y cuenta con diferentes unidades hidrológicas protegidas, en el mismo ensayo de campo con melón bajo riego por goteo se evaluó el riesgo de contaminación por nitratos tras la aplicación de diferentes dosis de compost bajo dos regímenes de riego, riego ajustado a las necesidades del cultivo (90 ó 100% de la evapotranspiración del cultivo (ETc)) o riego excedentario (120% ETc). A lo largo del ciclo de cultivo se estimó semanalmente el drenaje mediante la realización de un balance hídrico, así como se tomaron muestras de la solución de suelo y se determinó su concentración de nitratos. Para evaluar el riesgo de contaminación de las aguas subterráneas asociado con estas prácticas, se utilizaron algunos índices medioambientales para determinar la variación en la calidad del agua potable (Índice de Impacto (II)) y en la concentración de nitratos del acuífero (Índice de Impacto Ambiental (EII)). Para combinar parámetros medioambientales con parámetros de producción, se calculó la eficiencia de manejo. Se observó que la aplicación de compost bajo un régimen de riego ajustado no aumentaba el riesgo de contaminación de las aguas subterráneas incluso con la aplicación de la dosis más alta. Sin embargo, la aplicación de grandes cantidades de compost combinada con un riego excedentario supuso un incremento en el N lixiviado a lo largo del ciclo de cultivo, mientras que no se obtuvieron mayores producciones con respecto al riego ajustado. La aplicación de residuos de la industria vinícola y alcoholera como fuente de P fue evaluada en suelos calizos caracterizados por una alta capacidad de retención de P, lo cual en algunos casos limita la disponibilidad de este nutriente. Para ello se llevó a cabo otro ensayo de incubación con dos suelos de diferente textura, con diferente contenido de carbonato cálcico, hierro y con dos niveles de P disponible; a los que se aplicaron diferentes materiales procedentes de estas industrias (con y sin compostaje previo) aportando diferentes cantidades de P. A lo largo del tiempo se analizó el P disponible del suelo (P Olsen) así como el pH y el carbono orgánico disuelto. Al final de la incubación, con el fin de estudiar los cambios producidos por los diferentes residuos en el estado del P del suelo se llevó a cabo un fraccionamiento del P inorgánico del suelo, el cual se separó en P soluble y débilmente enlazado (NaOH-NaCl-P), P soluble en reductores u ocluido en los óxidos de Fe (CBD-P) y P poco soluble precipitado como Ca-P (HCl-P); y se determinó la capacidad de retención de P así como el grado de saturación de este elemento en el suelo. En este ensayo se observó que, dada la naturaleza caliza de los suelos, la influencia de la cantidad de P aplicado con los residuos en el P disponible sólo se producía al comienzo del periodo de incubación, mientras que al final del ensayo el incremento en el P disponible del suelo se igualaba independientemente del P aplicado con cada residuo, aumentando el P retenido en la fracción menos soluble con el aumento del P aplicado. Por el contrario, la aplicación de materiales orgánicos menos estabilizados y con un menor contenido en P, produjo un aumento en las formas de P más lábiles debido a una disolución del P retenido en la fracción menos lábil, lo cual demostró la influencia de la materia orgánica en los procesos que controlan el P disponible en el suelo. La aplicación de residuos aumentó el grado de saturación de P de los suelos, sin embargo los valores obtenidos no superaron los límites establecidos que indican un riesgo de contaminación de las aguas. La influencia de la aplicación de residuos orgánicos en las formas de P inorgánico y orgánico del suelo se estudió además en un suelo ácido de textura areno francosa tras la aplicación en campo a largo plazo de estiércol vacuno y de compost obtenido a partir de biorresiduos, así como la aplicación combinada de compost y un fertilizante mineral (superfosfato tripe), en una rotación de cultivos. En muestras de suelo recogidas 14 años después del establecimiento del experimento en campo, se determinó el P soluble y disponible, la capacidad de adsorción de P, el grado de saturación de P así como diferentes actividades enzimáticas (actividad deshidrogenasa, fosfatasa ácida y fosfatasa alcalina). Las diferentes formas de P orgánico en el suelo se estudiaron mediante una técnica de adición de enzimas con diferentes substratos específicos a extractos de suelo de NaOH-EDTA, midiendo el P hidrolizado durante un periodo de incubación por colorimetría. Las enzimas utilizadas fueron la fosfatasa ácida, la nucleasa y la fitasa las cuales permitieron identificar monoésteres hidrolizables (monoester-like P), diésteres (DNA-like P) e inositol hexaquifosfato (Ins6P-like P). La aplicación a largo plazo de residuos orgánicos aumentó el P disponible del suelo proporcionalmente al P aplicado con cada tipo de fertilización, suponiendo un mayor riesgo de pérdidas de P dado el alto grado de saturación de este suelo. La aplicación de residuos orgánicos aumentó el P orgánico del suelo resistente a la hidrólisis enzimática, sin embargo no influyó en las diferentes formas de P hidrolizable por las enzimas en comparación con las observadas en el suelo sin enmendar. Además, las diferentes formas de P orgánico aplicadas con los residuos orgánicos no se correspondieron con las analizadas en el suelo lo cual demostró que éstas son el resultado de diferentes procesos en el suelo mediados por las plantas, los microorganismos u otros procesos abióticos. En este estudio se encontró una correlación entre el Ins6P-like P y la actividad microbiana (actividad deshidrogenasa) del suelo, lo cual refuerza esta afirmación. Por último, la aplicación de residuos orgánicos como fuente de N y P en la agricultura se evaluó agronómicamente en un escenario real. Se estableció un experimento de campo para evaluar el compost procedente de residuos de bodegas y alcoholeras en el mismo cultivo de melón utilizado en el estudio de la mineralización y lixiviación de N. En este experimento se estudió la aplicación de tres dosis de compost: 1, 2 y 3 kg de compost por metro lineal de plantación correspondientes a 7, 13 y 20 t de compost por hectárea respectivamente; y se estudió el efecto sobre el crecimiento de las plantas, la acumulación de N y P en la planta, así como la producción y calidad del cultivo. La aplicación del compost produjo un ligero incremento en la biomasa vegetal acompañado por una mejora significativa de la producción con respecto a las parcelas no enmendadas, obteniéndose la máxima producción con la aplicación de 2 kg de compost por metro lineal. Aunque los efectos potenciales del N y P fueron parcialmente enmascarados por otras entradas de estos nutrientes en el sistema (alta concentración de nitratos en el agua de riego y ácido fosfórico suministrado por fertirrigación), se observó una mayor acumulación de P uno de los años de estudio que resultó en un aumento en el número de frutos en las parcelas enmendadas. Además, la mayor acumulación de N y P disponible en el suelo al final del ciclo de cultivo indicó el potencial uso de estos materiales como fuente de estos nutrientes. ABSTRACT Nitrogen (N) and phosphorus (P) are essential nutrients in crop production. The development of synthetic fertilizers during the 20th century allowed an intensification of the agriculture increasing crop yields but in turn the great input of nutrients has resulted in some cases in inefficient systems with higher losses to the environment. Regarding P, the scarcity of phosphate rock reserves necessary for the production of phosphate fertilizers aggravates this problem. The use of organic wastes in agriculture as a source of N and P is a good option of management that allows to value the large amount of wastes generated. However, it is important to understand the processes occurring in the soil after application of these materials, as they affect the availability of nutrients that can be used by the crop and the nutrient losses from agricultural systems that can cause problems of contamination. Although soil N dynamic has been more studied than P, the important concern of nitrate pollution in Nitrate Vulnerable Zones requires the evaluation of those management practices that could aggravate this situation, and in the case of organic wastes, the evaluation of the agronomic and environmental response after application of materials with a high N content (such as wastes from winery and distillery industries). On the other hand, due to the complexity of soil P cycle and the reactions that occur in soil, there is less knowledge about the factors that can influence its dynamics in the soil-plant system, which means new opportunities of study regarding the evaluation of the agricultural use of organic wastes. Taking into account the previous knowledge of each nutrient and the specific needs of study, in this Thesis we have evaluated: (1) the effect of the application of wastes from the winery and distillery industries on N dynamics from the agronomic and environmental viewpoint in a vulnerable zone; and (2) the factors that influence P availability in soils after the application of organic wastes. With this purposes, incubations were carried out in laboratory conditions as well as field trials that allow to assess the dynamic of these nutrients in real conditions. Soil incubations under controlled moisture and temperature conditions to determine N mineralization are commonly used to estimate N availability for crops together with the environmental risk. Therefore, a laboratory incubation was conducted in order to determine the N mineralization rate of a compost made from wastes generated in the winery and distillery industries, widely distributed in Castilla-La Mancha, a region with significant problems of aquifers contamination by nitrates. Three increasing doses of compost corresponding to 230, 460 and 690 kg of total N per hectare were mixed with a sandy clay loam soil collected in this area. The evolution of mineral N in soil over time was adjusted to a nonlinear regression model, obtaining low values of potentially mineralizable N and low constants of mineralization, indicating that it is a material resistant to mineralization with a slow release of N, with only 1.61, 1.33 and 1.21% of total N applied being mineralized with each increasing dose of compost (for a period of six months). Furthermore, N mineralization after the application of this material was also evaluated in field conditions by carrying out a N balance during two growing seasons (2011 and 2012) of a melon crop under drip irrigation, a crop and management very characteristic of the area of study. The mineralization constants obtained in the laboratory were adjusted to the actual temperatures observed in the field to predict N mineralized during each growing season, however, this model generally overestimated the N mineralization observed in the field, because of the influence of other factors not taken into account for this prediction, as N accumulated in soil, the plant effect or the fluctuations of temperature and moisture. The fitting of the laboratory data to the model as well as the predictions of N mineralized in the field were better when considering N mineralized from the soil-compost mixture rather than when N mineralized from compost was isolated, underlining the important role of the soil on N mineralization from organic wastes. Since the area of study was declared vulnerable to nitrate pollution and is situated between different protected hydrological units, the risk of nitrate pollution after application of different doses compost was evaluated in the same field trial with melon under two irrigation regimes, irrigation adjusted to the crop needs (90 or 100% of the crop evapotranspiration (ETc)) or excedentary irrigation (120% ETc). Drainage was estimated weekly throughout the growing season by conducting a water balance, samples of the soil solution were taken and the concentration of nitrates was determined. To assess the risk of groundwater contamination associated with these practices, some environmental indices were used to determine the variation in the quality of drinking water (Impact Index (II)) and the nitrates concentration in the groundwater (Environmental Impact Index (EII)). To combine environmental parameters together with yield parameters, the Management Efficiency was calculated. It was observed that the application of compost under irrigation adjusted to the plant needs did not represent a higher risk of groundwater contamination even with the application of the highest doses. However, the application of large amounts of compost combined with an irrigation surplus represented an increase of N leaching during the growing season compared with the unamended plots, while no additional yield with respect to the adjusted irrigation strategy is obtained. The application of wastes derived from the winery and distillery industry as source of P was evaluated in calcareous soils characterized by a high P retention capacity, which in some cases limits the availability of this nutrient. Another incubation experiment was carried out using two soils with different texture, different calcium carbonate and iron contents and two levels of available P; to which different materials from these industries (with and without composting) were applied providing different amounts of P. Soil available P (Olsen P), pH and dissolved organic carbon were analyzed along time. At the end of the incubation, in order to study the changes in soil P status caused by the different residues, a fractionation of soil inorganic P was carried out, which was separated into soluble and weakly bound P (NaOH-NaCl- P), reductant soluble P or occluded in Fe oxides (CBD-P) and P precipitated as poorly soluble Ca-P (HCl-P); and the P retention capacity and degree of P saturation were determined as well. Given the calcareous nature of the soils, the influence of the amount of P applied with the organic wastes in soil available P only occurred at the beginning of the incubation period, while at the end of the trial the increase in soil available P equalled independently of the amount of P applied with each residue, increasing the P retained in the least soluble fraction when increasing P applied. Conversely, the application of less stabilized materials with a lower content of P resulted in an increase in the most labile P forms due to dissolution of P retained in the less labile fraction, demonstrating the influence of organic matter addition on soil P processes that control P availability in soil. As expected, the application of organic wastes increased the degree of P saturation in the soils, however the values obtained did not exceed the limits considered to pose a risk of water pollution. The influence of the application of organic wastes on inorganic and organic soil P forms was also studied in an acid loamy sand soil after long-term field application of cattle manure and biowaste compost and the combined application of compost and mineral fertilizer (triple superphosphate) in a crop rotation. Soil samples were collected 14 years after the establishment of the field experiment, and analyzed for soluble and available P, P sorption capacity, degree of P saturation and enzymatic activities (dehydrogenase, acid phosphatase and alkaline phosphatase). The different forms of organic P in soil were determined by using an enzyme addition technique, based on adding enzymes with different substrate specificities to NaOH-EDTA soil extracts, measuring the hydrolyzed P colorimetrically after an incubation period. The enzymes used were acid phosphatase, nuclease and phytase which allowed to identify hydrolyzable monoesters (monoester-like P) diesters (DNA-like P) and inositol hexakisphosphate (Ins6P-like P). The long-term application of organic wastes increased soil available P proportionally to the P applied with each type of fertilizer, assuming a higher risk of P losses given the high degree of P saturation of this soil. The application of organic wastes increased soil organic P resistant to enzymatic hydrolysis, but no influence was observed regarding the different forms of enzyme hydrolyzable organic P compared to those observed in the non-amended soil. Furthermore, the different forms of organic P applied with the organic wastes did not correspond to those analyzed in the soil which showed that these forms in soil are a result of multifaceted P turnover processes in soil affected by plants, microorganisms and abiotic factors. In this study, a correlation between Ins6P-like P and the microbial activity (dehydrogenase activity) of soil was found, which reinforces this claim. Finally, the application of organic wastes as a source of N and P in agriculture was evaluated agronomically in a real field scenario. A field experiment was established to evaluate the application of compost made from wine-distillery wastes in the same melon crop used in the experiments of N mineralization and leaching. In this experiment the application of three doses of compost were studied: 1 , 2 and 3 kg of compost per linear meter of plantation corresponding to 7, 13 and 20 tonnes of compost per hectare respectively; and the effect on plant growth, N and P accumulation in the plant as well as crop yield and quality was studied. The application of compost produced a slight increase in plant biomass accompanied by a significant improvement in crop yield with respect to the unamended plots, obtaining the maximum yield with the application of 2 kg of compost per linear meter. Although the potential effects of N and P were partially masked by other inputs of these nutrients in the system (high concentration of nitrates in the irrigation water and phosphoric acid supplied by fertigation), an effect of P was observed the first year of study resulting in a greater plant P accumulation and in an increase in the number of fruits in the amended plots. In addition, the higher accumulation of available N and P in the topsoil at the end of the growing season indicated the potential use of this material as source of these nutrients.

Bio-based polymer nanocomposites based on nylon 11 and WS2 inorganic nanotubes

Tungsten disulphide nanotubes (INT-WS2) have been successfully dispersed in a bio-based polyamide matrix (nylon 11) by conventional melt processing. The effect of INT-WS2 content on the morphology, thermal stability, crystallization behaviour and dynamic mechanical properties is investigated. The results indicate that these inorganic nanotubes can be efficiently incorporated into the bio-based polymer matrix without the need for modifiers or surfactants. Additionally, it is found that the non-isothermal crystallization behaviour of nylon 11/INT-WS2 depends on both the cooling rate and INT-WS2 concentration. In particular, crystallization kinetics results demonstrate that the nucleating activity of INTs plays a dominant role in accelerating the crystallization of nylon 11. This fact leads to the appearance of the more-disordered phase at higher temperature. More significantly, it was shown that these INT-WS2 nanocomposites can facilitate a good processability and cost efficiency, and will be of interest for many eco-friendly and medical applications.

The vibrational energy flow transition in organic molecules: Theory meets experiment

Most large dynamical systems are thought to have ergodic dynamics, whereas small systems may not have free interchange of energy between degrees of freedom. This assumption is made in many areas of chemistry and physics, ranging from nuclei to reacting molecules and on to quantum dots. We examine the transition to facile vibrational energy flow in a large set of organic molecules as molecular size is increased. Both analytical and computational results based on local random matrix models describe the transition to unrestricted vibrational energy flow in these molecules. In particular, the models connect the number of states participating in intramolecular energy flow to simple molecular properties such as the molecular size and the distribution of vibrational frequencies. The transition itself is governed by a local anharmonic coupling strength and a local state density. The theoretical results for the transition characteristics compare well with those implied by experimental measurements using IR fluorescence spectroscopy of dilution factors reported by Stewart and McDonald [Stewart, G. M. & McDonald, J. D. (1983) J. Chem. Phys. 78, 3907–3915].

Titration of chaos with added noise

Deterministic chaos has been implicated in numerous natural and man-made complex phenomena ranging from quantum to astronomical scales and in disciplines as diverse as meteorology, physiology, ecology, and economics. However, the lack of a definitive test of chaos vs. random noise in experimental time series has led to considerable controversy in many fields. Here we propose a numerical titration procedure as a simple “litmus test” for highly sensitive, specific, and robust detection of chaos in short noisy data without the need for intensive surrogate data testing. We show that the controlled addition of white or colored noise to a signal with a preexisting noise floor results in a titration index that: (i) faithfully tracks the onset of deterministic chaos in all standard bifurcation routes to chaos; and (ii) gives a relative measure of chaos intensity. Such reliable detection and quantification of chaos under severe conditions of relatively low signal-to-noise ratio is of great interest, as it may open potential practical ways of identifying, forecasting, and controlling complex behaviors in a wide variety of physical, biomedical, and socioeconomic systems.

Oxide Semiconductors For Organic Opto-electronic Devices

Development of transparent oxide semiconductors (TOS) from Earth-abundant materials is of great interest for cost-effective thin film device applications, such as solar cells, light emitting diodes (LEDs), touch-sensitive displays, electronic paper, and transparent thin film transistors. The need of inexpensive or high performance electrode might be even greater for organic photovoltaic (OPV), with the goal to harvest renewable energy with inexpensive, lightweight, and cost competitive materials. The natural abundance of zinc and the wide bandgap ($sim$3.3 eV) of its oxide make it an ideal candidate. In this dissertation, I have introduced various concepts on the modulations of various surface, interface and bulk opto-electronic properties of ZnO based semiconductor for charge transport, charge selectivity and optimal device performance. I have categorized transparent semiconductors into two sub groups depending upon their role in a device. Electrodes, usually 200 to 500 nm thick, optimized for good transparency and transporting the charges to the external circuit. Here, the electrical conductivity in parallel direction to thin film, i.e bulk conductivity is important. And contacts, usually 5 to 50 nm thick, are optimized in case of solar cells for providing charge selectivity and asymmetry to manipulate the built in field inside the device for charge separation and collection. Whereas in Organic LEDs (OLEDs), contacts provide optimum energy level alignment at organic oxide interface for improved charge injections. For an optimal solar cell performance, transparent electrodes are designed with maximum transparency in the region of interest to maximize the light to pass through to the absorber layer for photo-generation, plus they are designed for minimum sheet resistance for efficient charge collection and transport. As such there is need for material with high conductivity and transparency. Doping ZnO with some common elements such as B, Al, Ga, In, Ge, Si, and F result in n-type doping with increase in carriers resulting in high conductivity electrode, with better or comparable opto-electronic properties compared to current industry-standard indium tin oxide (ITO). Furthermore, improvement in mobility due to improvement on crystallographic structure also provide alternative path for high conductivity ZnO TCOs. Implementing these two aspects, various studies were done on gallium doped zinc oxide (GZO) transparent electrode, a very promising indium free electrode. The dynamics of the superimposed RF and DC power sputtering was utilized to improve the microstructure during the thin films growth, resulting in GZO electrode with conductivity greater than 4000 S/cm and transparency greater than 90 %. Similarly, various studies on research and development of Indium Zinc Tin Oxide and Indium Zinc Oxide thin films which can be applied to flexible substrates for next generation solar cells application is presented. In these new TCO systems, understanding the role of crystallographic structure ranging from poly-crystalline to amorphous phase and the influence on the charge transport and optical transparency as well as important surface passivation and surface charge transport properties. Implementation of these electrode based on ZnO on opto-electronics devices such as OLED and OPV is complicated due to chemical interaction over time with the organic layer or with ambient. The problem of inefficient charge collection/injection due to poor understanding of interface and/or bulk property of oxide electrode exists at several oxide-organic interfaces. The surface conductivity, the work function, the formation of dipoles and the band-bending at the interfacial sites can positively or negatively impact the device performance. Detailed characterization of the surface composition both before and after various chemicals treatment of various oxide electrode can therefore provide insight into optimization of device performance. Some of the work related to controlling the interfacial chemistry associated with charge transport of transparent electrodes are discussed. Thus, the role of various pre-treatment on poly-crystalline GZO electrode and amorphous indium zinc oxide (IZO) electrode is compared and contrasted. From the study, we have found that removal of defects and self passivating defects caused by accumulation of hydroxides in the surface of both poly-crystalline GZO and amorphous IZO, are critical for improving the surface conductivity and charge transport. Further insight on how these insulating and self-passivating defects cause charge accumulation and recombination in an device is discussed. With recent rapid development of bulk-heterojunction organic photovoltaics active materials, devices employing ZnO and ZnO based electrode provide air stable and cost-competitive alternatives to traditional inorganic photovoltaics. The organic light emitting diodes (OLEDs) have already been commercialized, thus to follow in the footsteps of this technology, OPV devices need further improvement in power conversion efficiency and stable materials resulting in long device lifetimes. Use of low work function metals such as Ca/Al in standard geometry do provide good electrode for electron collection, but serious problems using low work-function metal electrodes originates from the formation of non-conductive metal oxide due to oxidation resulting in rapid device failure. Hence, using low work-function, air stable, conductive metal oxides such as ZnO as electrons collecting electrode and high work-function, air stable metals such as silver for harvesting holes, has been on the rise. Devices with degenerately doped ZnO functioning as transparent conductive electrode, or as charge selective layer in a polymer/fullerene based heterojunction, present useful device structures for investigating the functional mechanisms within OPV devices and a possible pathway towards improved air-stable high efficiency devices. Furthermore, analysis of the physical properties of the ZnO layers with varying thickness, crystallographic structure, surface chemistry and grain size deposited via various techniques such as atomic layer deposition, sputtering and solution-processed ZnO with their respective OPV device performance is discussed. We find similarity and differences in electrode property for good charge injection in OLEDs and good charge collection in OPV devices very insightful in understanding physics behind device failures and successes. In general, self-passivating surface of amorphous TCOs IZO, ZTO and IZTO forms insulating layer that hinders the charge collection. Similarly, we find modulation of the carrier concentration and the mobility in electron transport layer, namely zinc oxide thin films, very important for optimizing device performance.

Nanocompósito de poliestireno reciclado, bentonita sódica e hemi-hidrato de sulfato de cálcio: obtenção e caracterização.

Nesta Tese foram preparados, em solução, filmes híbridos de argila e poliestireno provenientes de copos descartáveis comercializados no mercado brasileiro, com acetato de etila e glicerol. Posteriormente, foi adicionado o Hemi-hidrato de sulfato de cálcio como carga de reforço. Tanto a argila quanto o glicerol, assim como o hemihidrato de sulfato de cálcio, foram utilizados nos percentuais relativos à massa do poliestireno fragmentado correspondendo a 1%,2%, 3%,4%, 5% e 7%. Dos filmes, nos percentuais 3, 4, 5 e 7, exclui-se o percentual de 4% e os demais foram fragmentados e submetidos a extrusão, com resfriamento natural, à seco, produzindo-se grãos com os quais foi avaliado o índice de fluidez e injetados para a moldagem de corpos de prova rígidos. O desempenho dos corpos rígidos, foi comparado com os resultados do HIPS 484, e o GPPS comercializados no mercado brasileiro. Os filmes foram caracterizados por difração de raios X, microscopia eletrônica de varredura (MEV), calorimetria exploratória diferencial (DSC), além dos testes de resistência à tração, fluorescência de raios X, EDS e FTIR. Amostra do filme, ultrafino, obtido a partir da solução com o percentual de 5% foi observada ao microscópio ótico e no microscópio eletrônico de transmissão, assim como amostras de corpos rígidos microtomizadas. Nos corpos rígidos, além das análises instrumentais citadas, foram avaliadas a resistência à flexão, modulo de flexão, resistência à tração, alongamento e resistência ao impacto Izod. O desempenho sob chama foi avaliado em amostras de filme e também do corpo rígido. Resultados do DRX, e da MET foram coerentes com a bibliografia para nanocompósitos argila-polímero e, associado às respostas dos demais ensaios, indicaram um material de boa qualidade morfológica e boas propriedades mecânicas comparadas ao HIPS 484 e ao GPPS. Sob a chama o material produzido apresentou maior resistência à queima avaliado pela quantidade aparente de material residual para um mesmo tempo sob fogo. Constatou-se, também, uma boa dispersão das cargas na matriz polimérica, assim como uma adequada interação entre os elementos orgânicos e inorgânicos do material, a delaminação parcial da argila e quebra da estrutura do hemi-hidrato. Isto resultou em um bom desempenho mecânico e térmico do compósito que pode ser atribuído, tanto a uma forte influência dos íons metálicos presentes nas cargas inorgânicas, quanto às adições presentes na formulação dos copos descartáveis.